CN100480335C - Air drying waterborne resin composition - Google Patents

Air drying waterborne resin composition Download PDF

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CN100480335C
CN100480335C CNB2003801020394A CN200380102039A CN100480335C CN 100480335 C CN100480335 C CN 100480335C CN B2003801020394 A CNB2003801020394 A CN B2003801020394A CN 200380102039 A CN200380102039 A CN 200380102039A CN 100480335 C CN100480335 C CN 100480335C
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air
dry
acid
resin composition
based resin
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CN1708558A (en
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B·黑格曼
H·比约恩贝里
B·米德尔夫
D·B·雅姆
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Perstorp Specialty Chemicals AB
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/01—Hydrocarbons
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)
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  • Road Signs Or Road Markings (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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  • Polyesters Or Polycarbonates (AREA)
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Abstract

An air drying waterborne resin composition is disclosed. Said resin composition comprises at least one amphiphilic air drying dendritic polymer, at least one non-amphiphilic air drying alkyd resin, at least one drier initiating and/or promoting autoxidation, and water, and optionally at least one anionic and/or nonionic surfactant, and/or at least one coalescent agent. Said at least one amphiphilic air drying dendritic polymer is built up from a polyhydric dendritic core polymer having terminal hydroxyl groups and at least one unsaturated carboxylic acid and at least one adduct, obtainable by addition of a monoalkylated polyethylene glycol to a dicarboxylic acid or anhydride and/or a diisocyanate, each bonded to at least one terminal hydroxyl group in said polyhydric dendritic core polymer.

Description

Air-dry water-based resin composition
The present invention relates to water-based resin composition, resin emulsion for example, dispersion or solution comprise air-dry branch-shape polymer of at least a amphipathic and at least a non-amphipathic air-drying resin, short oil for example, the Synolac of middle oil or long oil.On the other hand, the present invention relates to produce the method for described resin combination and described amphipathic branch-shape polymer purposes as dispersion resin.
Water-based paint or resin are the coating or the resins of dilute with water before use.Although the volatile matter of main amount is a water, most of water-based paint contains some solvents.Latex paint occupies dominant position indoor and outdoor architecture market with flat, semi-gloss and gloss paint.Aqueous based systems also is used in the industrial maintenance coatings based on water-soluble or dispersion resin system.Another kind of waterborne alkyd resin and the polyester of comprising.Although no longer be the resin that is used for the base class of coating, Synolac still is very important and has made the numerous Synolac of kind.And some non-exsiccant Synolac are used as softening agent in the paint or crosslinked with melamine-formaldehyde resin in baking enamel, and major portion is the auto-oxidatively drying Synolac that is used for the air-dry and coating that forced drying is used of environment.The main advantage of Synolac is the low and comparatively safe application characteristic of cost.
Waterborne alkyd resin and vibrin have the acid number of typical terminal hydroxy group and carboxyl and 40-60mgKOH/g.In order to make this resin can be with lower gelling risk duplication of production, the reactivity of different carboxyls must be significantly different.Use trimellitic acid 1,2-anhydride to utilize the higher level of reactivity of anhydride group nearly when reaction finishes at a lower temperature.Another kind method for example uses dimethylol propionic acid to be used as the part of glycol in the preparation of polyester.Higher sterically hindered carboxylic esterification ratio is as slow from the carboxyl of m-phthalic acid and hexanodioic acid.After reaction proceeded to suitable acid number, Synolac or polyester for example were dissolved in the glycol ethers.Amine or ammonium are used for and acidic group, and colo(u)rant dispersion is in resin solution, and for example tensio-active agent and siccative and this aqueous coating are reduced to application viscosity to add additive.Resin in the dilution coating is not in solution, but forms by solvent and water swollen aggregate.This system is subject to their relatively easy hydrolysis storage time.Usually can realize the stability in storage improved by adding a large amount of tensio-active agents, yet tensio-active agent can increase the water vapor sensitive of dry coating.
Waterborne alkyd resin as discussed above obtained can with the drying property that compares favourably with traditional solvent-based alkyd routine.Yet they are not extensive use of, because film character is tending towards poorer than those of solvent-based alkyd, especially in air-dry system.Waterborne alkyd resin typically as top disclosed, has high acid value and be neutralized to water-dilutable, and conventional Synolac have low acid number, and if when in the time can not get water-dilutable.By the evaporation volatile matter with pass through the cross-linking reaction of environment automatic oxidation reaction or elevated temperature subsequently and film forming.Solvent promptly promotes film forming and improves film quality for example as flocculation agent.Relative humidity can have remarkable influence to dry behavior and film quality.The good water-based formulation of performance has defective under high humidity when applying under drying conditions.The speed of water evaporation is much slow when high humidity, but solvent evaporation continues.This causes solvent occurring at film forming critical stage and exhausts and therefore poor film progress.Be used for and the slow loss of the amine of high acid value or ammonium causes short period of time hypersensitivity to water.Even in absolutely dry film, the existence of unreacted carboxyl causes having the water-proof film of the relative mistake of the application that limits them.Water base and solvent-based alkyd fully discloses and is discussed at " Surface Coatings Technology " Vol.VI " Waterborne andSolvent Based Alkyds and their End User Applications ", by N.Tuck, John Wiley and Sons 2000 SITA Technology Ltd..
Latex and water-soluble polymers are by the mechanism drying of the Synolac that is different from.Latex is made of the dispersive polymer beads in water, and film forming takes place when particle aggregation is set up a continuous film.Particle must have enough low glass transition temp (Tg), also to bond mutually in the application of temperature current downflow.Flocculation agent is used as transient plasticizer in becoming mem stage, promote Tg reduction and mobile, evaporates after film forming taking place then.The most frequently used flocculation agent is slow vapo(u)rability glycol ethers and glycol ether-ether.Glycol for example ethylene glycol or propylene glycol adds usually and is used for stability in storage and frost resistance.
The invention discloses a kind of novel water-based resin combination, for example air-drying resin emulsion, dispersion or solution, comprise that the air-dry branch-shape polymer of amphipathic is used for the air-dry Synolac of non-amphipathic as dispersion resin, the for example common conventional Synolac that in solvent substrate system, uses, thus the inferior position of aforesaid waterborne alkyd resin is reduced or reduction substantially.
Water-based resin composition of the present invention contains the air-dry branch-shape polymer of at least a amphipathic, at least a non-amphipathic air-drying resin, at least a initiation and/or promote autoxidizable siccative, and water.Described resin combination can comprise at least a negatively charged ion and/or the nonionogenic tenside as optional components in addition, and/or at least a flocculation agent.
The air-dry branch-shape polymer of amphiphilic is non-ionic and self-emulsifying, and is made of a kind of dendroid core polymkeric substance, has terminal hydroxy group, and involved have unsaturated carboxyl and the hydrophobic chain of air-dry character and the combination institute chain extension of hydrophilic polyglycol chain are provided.The amphipathic branch-shape polymer is used as dry dispersion resin in resin combination and stablizer is used for for example conventional Synolac that typically is used for solvent substrate system of emulsification.
The air-dry branch-shape polymer of amphipathic is non-ionic and self-emulsifying, by have at least 4 terminal hydroxy group and therefore hydroxy functionality (f) be at least 4, for example 8,16,32 or 64, poly-hydroxy dendroid core polymkeric substance, at least a at least one and the carboxylic acid and at least a at least one and the adducts of f-1 described terminal hydroxy group at the most of being bonded to equally of f-1 described terminal hydroxy group at the most of being bonded to, this adducts can add on a kind of acid anhydrides of dicarboxylic acid, a kind of dicarboxylic acid or a kind of vulcabond by a kind of monoallcylated polyethylene glycol and obtain.
The dendroid core polymkeric substance of described amphipathic branch-shape polymer is for example at WO93/17060 in various embodiment, WO93/18079, WO96/07688, WO96/12754, WO99/00439, WO99/00440, disclosed poly-hydroxy branch-shape polymer among WO00/56802 and the WO02/40572.Described poly-hydroxy dendroid core polymkeric substance most preferably can be by at least a two in described embodiment, three or the poly-hydroxy monocarboxylic acid add to a kind of two, three or the poly-hydroxy core molecules on obtain, both mol ratios are to obtain comprising that a core molecules and at least one are bonded to described two, three or the poly-hydroxy core molecules on the poly-hydroxy branch-shape polymer in branching generation, maybe can be by two, three or at least a trimethylene oxide open loop of polyol add to a kind of two, three or the poly-hydroxy core molecules on obtain, both mol ratios be obtain comprising a core molecules and at least one be bonded to described two, three or the poly-hydroxy core molecules on the poly-hydroxy branch-shape polymer in branching generation.
Described two, three or the poly-hydroxy core molecules most preferably be 1, w-glycol, 5-hydroxyl-1, the 3-diox, 5-hydroxyalkyl-1,3-diox, 5-alkyl-5-hydroxyalkyl-1, the 3-diox, 5,5-two (hydroxyalkyl)-1, the 3-diox, 2-alkyl-1, ammediol, 2,2-dialkyl group-1, ammediol, 2-hydroxyl-1, ammediol, 2-hydroxyl-2-alkyl-1, ammediol, 2-hydroxyalkyl-2-alkyl-1, ammediol, 2,2-two (hydroxyalkyl)-1, ammediol, described two, three or the dimer of polyhydroxy-alcohol, tripolymer or polymkeric substance, or at least a oxirane and described two, three or polyhydroxy-alcohol or described dimer, the reaction product of tripolymer or polymkeric substance.
Described two, three or the poly-hydroxy monocarboxylic acid most preferably be 2, the 2-hydroxymethyl propionic acid, α, α-two (hydroxymethyl) butyric acid, α, α, α-three (hydroxymethyl) acetate, α, α-two (hydroxymethyl) valeric acid, α, α-two (hydroxymethyl) propionic acid, α, alpha-dihydroxy-propionic acid and/or 3, the 5-resorcylic acid.
Described trimethylene oxide most preferably is 3-alkyl-3-(hydroxyalkyl) trimethylene oxide, 3,3-two (hydroxyalkyl) trimethylene oxide, 3-alkyl-3-(hydroxy alkoxy base) trimethylene oxide, 3-alkyl-3-(hydroxy alkoxy alkyl) trimethylene oxide or 3-alkyl-3-(hydroxyalkyl) trimethylene oxide, 3,3-two (hydroxyalkyl) trimethylene oxide, dimer, tripolymer or the polymkeric substance of 3-alkyl-3-(hydroxy alkoxy base) trimethylene oxide or 3-alkyl-3-(hydroxy alkoxy alkyl) trimethylene oxide.
The described unsaturated carboxylic acid that adds on the described poly-hydroxy dendroid core polymkeric substance by reaction is aliphatic linearity or the branching lipid acid that for example has 8-24 carbon atom on its main carbochain in the various different embodiments of amphipathic branch-shape polymer, tall oil fatty acid for example, soya fatty acid, safflower lipid acid, Sunflower Receptacle lipid acid, cottonseed lipid acid, castor-oil plant lipid acid, oleic acid, linolic acid and/or linolenic acid.Other suitable unsaturated carboxylic acid is from for example with one or more described lipid acid bonded vinyl acids finding, for example vinylformic acid, methacrylic acid and/or Ba Dousuan.
The described adducts that adds on the described poly-hydroxy branch-shape polymer by reaction preferably and is advantageously had molecular weight and is at least 500 by at least a, the monoallcylated polyethylene glycol of 500-2500 or 700-1500 for example, with at least a linearity or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid or corresponding acid anhydrides, hexanodioic acid for example, nonane diacid, fumaric acid, maleic anhydride, phthalic acid or acid anhydrides, m-phthalic acid, the tetrahydro-phthalic anhydride, the hexahydro-phthalic anhydride, succsinic acid or acid anhydrides, and/or sebacic acid constitutes.Described monoallcylated polyethylene glycol most preferably is a monomethylated polyethylene glycol.
The described at least a non-amphipathic Synolac that is included in the resin combination of the present invention is a short oil, and the air-dry Synolac of middle oil and/or long oil for example typically is used in the conventional Synolac of solvent-based resin composition.
The preferred weight ratio of amphipathic branch-shape polymer and non-amphipathic resin is 1: 99 to 99: 1, for example 50:50,10:90,20:80,70:30,90:10,80:20 or 70:30.Most preferred weight ratio is the amphipathic branch-shape polymer of 20-30% weight and the non-amphipathic resin of 70-80% weight typically.The amphipathic branch-shape polymer can be used as dispersion resin in addition and advantageously and is used for pigment paste.
Be included in the described at least a siccative metal drier preferably in embodiments in the resin combination of the present invention, Pb for example, Zr, Co, Li, K, Mn or Mg siccative or their combination, for example octylate and/or naphthenate, with for example 0.01-0.3%, amount as 0.05-0.1% is mixed, and in the metal on the solid resin, it is air-dry branch-shape polymer of solid amphipathic and the non-amphipathic air-drying resin of solid.
Described optional tensio-active agent, if present, aptly with 1-5%, for example the amount of 2-10% weight is mixed, and calculates based on air-dry branch-shape polymer of described at least a amphipathic and described at least a non-amphipathic air-drying resin.
On the other hand, the present invention relates to produce the method for air-dry water-based resin composition as disclosed above.Described method comprises:
I) described air-dry branch-shape polymer, described air-drying resin and randomly described flocculation agent be at 40-80 ℃, for example 50-70 ℃ or 50-60 ℃ of mixing, and up to obtaining uniform mixture,
Ii) add and mix described siccative and randomly described tensio-active agent and/or other additive, neutralizing agent for example, flowing agent and flow agent,
Iii) with described component at 40-80 ℃, for example 50-70 ℃ or 50-60 ℃, mixed for example 10-60 minute, as 20-40 or 20-30 minute and
Iv) under violent stirring, with for example 40-80 ℃ of hot water, the water of 50-70 ℃ or 50-60 ℃ adds lentamente up to desired final solid content, for example 40-50%, and/or viscosity, and holding temperature is at 40-80 ℃ simultaneously, for example 50-70 ℃ or 50-60 ℃.
A kind of neutralizing agent, for example amine or ammonia, can add with in and remaining acidic group in described air-dry Synolac and/or described air-dry branch-shape polymer basically.
Of the present invention further aspect, the present invention relates to be used for non-amphipathic air-drying resin as water dispersed resin as the air-dry branch-shape polymer of amphipathic as described in disclosed herein, for example described conventional Synolac, and/or be used for the purposes of pigment and/or filler as dispersion resin.
The air-dry branch-shape polymer of amphipathic can be as dispersion resin with from described conventional alkyd resin production waterborne alkyd resin coating.Can obtain based on long oil the surfactant-free of middle oil or short-oil alkyd or solvent-free aqueous based systems.
Need not to describe in further detail, should think that those skilled in the art utilize above-mentioned description can farthest utilize the present invention.Therefore, to be interpreted into only be exemplary and the other parts of limit publicity content never in any form for following preferred specific embodiments.Among the embodiment 1-19 below, explained the preparation of the component that comprises among the present invention, embodiment of the present invention and simultaneous test.
Embodiment 1: the poly-alkoxylation adducts that uses among the synthetic embodiment 2.
Embodiment 2: synthetic amphipathic branch-shape polymer according to embodiments of the present invention, by poly-hydroxy dendroid core polymkeric substance, lipid acid and the adducts that obtains in embodiment 1 constitute.
Embodiment 3: synthetic conventional middle long oil alkyd.
Embodiment 4: synthetic conventional short-oil alkyd.
Embodiment 5: prepare the water-based resin composition of surfactant-free according to embodiments of the present invention, be included in the product that obtains among the embodiment 2 and long oil alkyd that can be commercially available.
Embodiment 6: prepare water-based resin water-based resin composition according to embodiments of the present invention, comprise the product that obtains in embodiment 2 and 3.
Embodiment 7: preparation does not have the water-based resin composition of flocculation agent according to embodiments of the present invention, comprises the product that obtains in embodiment 2 and 3.
Embodiment 8: prepare water-based resin composition according to embodiments of the present invention, comprise the product that embodiment 2 and 4 obtains.
Embodiment 9: preparation does not have the water-based resin composition of flocculation agent according to embodiments of the present invention, comprises the product that obtains in embodiment 2 and 4.
Embodiment 10: preparation comprises the pigment paste of the product that obtains among the embodiment 2.
Embodiment 11: use the resin combination of embodiment 5 and the pigment paste of embodiment 10 to prepare white paint.
Embodiment 12: use the resin combination of embodiment 6 and the pigment paste of embodiment 10 to prepare white paint.
Embodiment 13: use the resin combination of embodiment 7 and the pigment paste of embodiment 10 to prepare white paint.
Embodiment 14: use the resin combination of embodiment 8 and the pigment paste of embodiment 10 to prepare white paint.
Embodiment 15: use the resin combination of embodiment 9 and the pigment paste of embodiment 10 to prepare white paint.
Embodiment 16: estimate the resin combination that obtains among the embodiment 5-7 with respect to drying property and film character according to the solvent-based alkyd of embodiment 3 and 4.
Embodiment 17: drying property and the film character of estimating the white paint that obtains among the embodiment 12-16.
Embodiment 18: preparation does not have the water-based resin composition of flocculation agent and tensio-active agent according to embodiments of the present invention, comprise use among the product that obtains among the embodiment 2 and the embodiment 5 can be commercially available long oil.
Embodiment 19: the Comparative Examples outside the scope of the invention.The medium oil alkyd resin that emulsification embodiment 3 obtains does not use the amphiphilic branch-shape polymer of embodiment 2, and uses used same additives packing material among the embodiment 6.
Embodiment 1
618g monomethylated polyethylene glycol (molecular weight 750g/mol) is packed in 11 the reaction flask of being furnished with agitator and is heated to 100 ℃.Apply vacuum and temperature now and be increased to 120 ℃, and add the 18.2g succinyl oxide.After about 30 minutes, when reaching the acid number of 66mgKOH/g, by the cool to room temperature stopped reaction.Final product at room temperature is the hypocrystalline solid.
Embodiment 2
Step 1: 246g
Figure C200380102039D00121
H20 (dendritic polyester of hydroxyl-functional, PerstorpSpecialty Chemicals AB, Sweden) and 440g Sunflower Receptacle lipid acid are packed into and are furnished with in 11 reaction flasks of agitator and Dean Stark water trap, and are heated to 125 ℃.Add 0.6g phenylformic acid, 0.07g now 4100 (esterifying catalyst) and dimethylbenzene, and temperature is elevated to 190 ℃ and kept about 5 hours.Acid number was 2.5mgKOH/g after described 5 hours and removes removal xylene under vacuum.By the cool to room temperature stopped reaction.
The product that obtains has hydroxyl value to be 62mgKOH/g and to be 1.84Pas 23 ℃ of viscosity.
Step 2: 340g step 1 products therefrom and 200g embodiment 1 gained adducts are packed into and are furnished with in 11 reaction flasks of agitator and Dean Stark water trap.Reaction mixture is heated to 180 ℃, and with dimethylbenzene and 0.05g
Figure C200380102039D00131
4100 (esterifying catalysts) join in the reaction mixture.Stopped reaction when acid number reaches 8.5mgKOH/g.Remove removal xylene under vacuum, product is cooled to 90 ℃ and adding 25g distilled water.
The air-dry branch-shape polymer of the amphipathic that obtains at room temperature is to have the liquid that viscosity is 12Pas and final acid number 5.7mgKOH/g.Molecular-weight average is 10032g/mol.
Embodiment 3
The 942g soya fatty acid pack into be furnished with agitator, in 21 reaction flasks of Dean Stark water trap and nitrogen wash and temperature be raised to 160 ℃.207g tetramethylolmethane, 394g Tetra hydro Phthalic anhydride and dimethylbenzene (azeotropic solvent) join the reactor neutral temperature and rise to 240 ℃ under nitrogen covers.Reaction is carried out continuously up to the acid number that reaches below the 15mgKOH/g.The product cool to room temperature.
The final acid number that the gained Synolac has is 7mgKOH/g, and hydroxyl value is that 134mgKOH/g and oily length are 62.9% (as tri-glyceride).
Embodiment 4
The 574g soya fatty acid pack into be furnished with agitator, in 21 reaction flasks of Dean Stark water trap and nitrogen wash and temperature be raised to 160 ℃.45g tetramethylolmethane, 462g TriMethylolPropane(TMP), 508g Tetra hydro Phthalic anhydride and dimethylbenzene (azeotropic solvent) join the reactor neutral temperature and rise to 240 ℃ under nitrogen covers.Reaction is carried out continuously up to the acid number that reaches below the 15mgKOH/g.The product cool to room temperature.
The final acid number that the gained Synolac has is 15mgKOH/g, and hydroxyl value is that 120mgKOH/g and oily length are 40% (as tri-glyceride).
Embodiment 5
Amphipathic branch-shape polymer, the 160g of 40g embodiment 2 gained is commercially available have oily length be 82% tallol long oil alkyd (
Figure C200380102039D00132
301-2007, McWortherInc.) (as tri-glyceride), 10g dipropylene glycol methyl ether and 11g dipropylene glycol n-butyl ether are encased in the 11 laboratory flasks of being furnished with agitator.Mixture heating up to 60 ℃ and and keeping in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00141
VXW6206 SolutiaInc.) and further continues to stir 10 minutes.Now slowly adding 319g in 15 minutes removes the warm water (50 ℃) that mineralizes and further continues stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The solid content that gained emulsion (water base air-drying resin composition) has is 38% and is 150mPas 23 ℃ of viscosity.Under 50 ℃ of at least one weeks of following emulsion-stabilizing and the room temperature stable at least 6 months.
Embodiment 6
The amphipathic branch-shape polymer of 60g embodiment 2 gained, the medium oil alkyd resin that 180g obtains in embodiment 3,7.5g dipropylene glycol methyl ether and 10g dipropylene glycol n-butyl ether are packed in 11 the laboratory flask of being furnished with agitator.Mixture heating up to 60 ℃ also keeps in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then, add 6g nonionogenic tenside (Triton X100) and mixing.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00142
VXW 6206, Solutia Inc.) and further continue to stir 10 minutes.In 15 minutes, slowly add now 236g and go the warm water (50 ℃) that mineralizes and further continuously stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The solid content that gained emulsion (water base air-drying resin composition) has is 38% and is 100mPas 23 ℃ of viscosity.50 ℃ of following at least 2 weeks of emulsion-stabilizing.
Embodiment 7
The medium oil alkyd resin that the amphipathic branch-shape polymer of 60g embodiment 2 gained and 180g obtain in embodiment 3 is packed in 11 the laboratory flask of being furnished with agitator.Mixture heating up to 60 ℃ also keeps in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then, add 12.5g nonionogenic tenside (Triton X100) and mixing.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00143
VXW6206 SolutiaInc.) and further continues to stir 10 minutes.Now slowly adding 243g in 15 minutes removes the warm water (50 ℃) that mineralizes and further continues stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The solid content that gained emulsion (water base air-drying resin composition) has is 50% and is 200mPas 23 ℃ of viscosity.50 ℃ of following at least 2 weeks of emulsion-stabilizing.
Embodiment 8
The amphipathic branch-shape polymer of 60g embodiment 2 gained, the short-oil alkyd of 180g embodiment 4 gained, 7.5g dipropylene glycol methyl ether and 10g dipropylene glycol n-butyl ether are packed in 11 the laboratory flask of being furnished with agitator.Mixture heating up to 60 ℃ also keeps in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then, add 6g nonionogenic tenside (Triton X100) and mixing.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00151
VXW6206, Solutia Inc.) and further continue to stir 10 minutes.In 15 minutes, slowly add now 239g and go the warm water (50 ℃) that mineralizes and further continuously stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The solid content that gained emulsion (water base air-drying resin composition) has is 48% and is 100mPas 23 ℃ of viscosity.50 ℃ of following at least 1 weeks of emulsion-stabilizing.
Embodiment 9
The short-oil alkyd that the amphipathic branch-shape polymer of 60g embodiment 2 gained and 180g obtain in embodiment 4 is packed in 11 the laboratory flask of being furnished with agitator.Mixture heating up to 60 ℃ also keeps in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then, add 12.5g nonionogenic tenside (Triton X100) and mixing.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00152
VXW6206, Solutia Inc.) and further continue to stir 10 minutes.Now slowly adding 243g in 15 minutes removes the warm water (50 ℃) that mineralizes and further continues stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The solid content that gained emulsion (water base air-drying resin composition) has is 50% and is 150mPas 23 ℃ of viscosity.50 ℃ of following at least 1 weeks of emulsion-stabilizing.
Embodiment 10
The amphiphilic polymer that 48g obtains in embodiment 2 is packed in 11 the laboratory flask of being furnished with agitator.5g dipropylene glycol n-butyl ether and 15g part neutral polycarboxylic acid polymkeric substance alkylammonium salt and polydimethylsiloxane (
Figure C200380102039D00153
WS DowInc) under agitation adds.In 15 minutes, add 210g warm water (50 ℃).Pack into high speed dissolver and in 15 minutes, add 75gTiO of the emulsion that 25g obtains 2(
Figure C200380102039D00154
2310, Kronos GmbH).Make dissolving continue to carry out again 30 minutes.
The viscosity of gained pigment paste is that 15Pas and solid content are 78% at 23 ℃.
Embodiment 11
The emulsion that 45g obtains in embodiment 5 is packed in 11 the laboratory flask of being furnished with agitator and is mixed with the pigment paste that 55g obtains in embodiment 10.Mixture at room temperature stirred 30 minutes.The white paint that obtains stored 24 hours before estimating dry and other character.
The white paint that obtains comprises water base air-drying resin composition, and the solid content that has is 60%, and pigment is 1.9:1 to the ratio of resin and is 150mPas 23 ℃ viscosity.
Embodiment 12
The emulsion that 45g obtains in embodiment 6 is packed in 11 the laboratory flask of being furnished with agitator and is mixed with the pigment paste that 55g obtains in embodiment 10.Mixture at room temperature stirred 30 minutes.The white paint that obtains stored 24 hours before estimating dry and other character.
The white paint that obtains comprises water base air-drying resin composition, and the solid content that has is 65%, and pigment is 1.6 to the ratio of resin: viscosity is 150mPas.
Embodiment 13
The emulsion that 45g obtains in embodiment 7 is packed in 11 the laboratory flask of being furnished with agitator and is mixed with the pigment paste that 55g obtains in embodiment 10.Mixture at room temperature stirred 30 minutes.The white paint that obtains stored 24 hours before estimating dry and other character.
The white paint that obtains comprises water base air-drying resin composition, and the solid content that has is 65%, and pigment is 1.6:1 to the ratio of resin and is 150mPas 23 ℃ viscosity.
Embodiment 14
The emulsion that 45g obtains in embodiment 8 is packed in 11 the laboratory flask of being furnished with agitator and is mixed with the pigment paste that 55g obtains in embodiment 10.Mixture at room temperature stirred 30 minutes.The white paint that obtains stored 24 hours before estimating dry and other character.
The white paint that obtains comprises water base air-drying resin composition, and the solid content that has is 65%, and pigment is 1.6:1 to the ratio of resin and is 200mPas 23 ℃ viscosity.
Embodiment 15
The emulsion that 45g obtains in embodiment 6 is packed in 11 the laboratory flask of being furnished with agitator and is mixed with the pigment paste that 55g obtains in embodiment 10.Mixture at room temperature stirred 30 minutes.The white paint that obtains stored 24 hours before estimating dry and other character.
The white paint that obtains comprises water base air-drying resin composition, and the solid content that has is 65%, and pigment is 1.6:1 to the ratio of resin and is 150mPas 23 ℃ viscosity.
Embodiment 16
The emulsion that obtains in embodiment 5-9 is that the dry property of water base air-drying resin composition is at Beck Koller TM(Sheen Instrument determines in UK) tester.Measurement of hardness is pendulum hardness and is expressed as
Figure C200380102039D00171
Second.
The Synolac that obtains in embodiment 3 and 4 (with reference to 1 and 2) is dissolved in the dimethylbenzene neutralization and is used as reference example.Use with water-based resin composition in identical siccative and the siccative of same amount, carry out same evaluation.
Time of drying:
With reference to 1 With reference to 2 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
The drying film, μ m 50-60 50-60 50-605 0-60 50-60 50-60 50-60
Inviscid, hour 12.5 4.5 5.5 2 1.5 5 4
Saturating doing, hour >24 14 20.5 6 5.5 22 21
Pendulum hardness:
Figure C200380102039D00172
Embodiment 17
The dry property of the white paint that obtains in embodiment 11-15 is at Beck Koller TM(Sheen Instrument UK) upward determines tester.Determine after dry 48 hours that gloss and measurement of hardness under 20 ° and 60 ° are pendulum hardness and are expressed as
Figure C200380102039D00173
Second.All lacquers apply with the wet-film thickness of 120 μ m.
Time of drying and gloss:
Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15
Inviscid, hour 3.5 0.4 0.4 2.5 2.4
Saturating doing, hour 18 4 4 16 16
20 ° of gloss 40 54 61 22 48
60 ° of gloss 75 88 89 66 75
Pendulum hardness:
Figure C200380102039D00181
Embodiment 18
The amphipathic branch-shape polymer of 40g embodiment 2 gained and 160g are commercially available have oily length be 82% tallol long oil alkyd (
Figure C200380102039D00182
301-2007, McWortherInc.) (as tri-glyceride) is encased in the 11 laboratory flasks of being furnished with agitator.Mixture heating up to 60 ℃ also keeps in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00183
VXW6206, Solutia Inc.) and further continue to stir 10 minutes.Now slowly adding 450g in 15 minutes removes the warm water (50 ℃) that mineralizes and further continues stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The solid content that gained emulsion (water base air-drying resin composition) has is 30% and is 300mPas 23 ℃ of viscosity.Stablized at least 6 months under the emulsion room temperature.
Embodiment 19
The medium oil alkyd resin of 240g embodiment 3 gained, 7.5g dipropylene glycol methyl ether and 10g dipropylene glycol n-butyl ether are packed in 11 the laboratory flask of being furnished with agitator.Mixture heating up to 60 ℃ also keeps in this temperature.Stir the mixture up to evenly, adjust to pH7.5 by adding dimethylethyl amine then, add 6g nonionogenic tenside (Triton X100) and mixing.Present adding 4gCo/Li/Zr siccative (
Figure C200380102039D00191
VXW6206, Solutia Inc.) and further continue to stir 10 minutes.Now slowly adding 236g in 15 minutes removes the warm water (50 ℃) that mineralizes and further continues stirring 20 minutes.The gained emulsion is cool to room temperature under agitation at last.
The gained emulsion is separated at room temperature 15 minutes.

Claims (20)

1. air-dry water-based resin composition, comprise the air-dry branch-shape polymer of at least a amphipathic, at least a non-amphipathic air-drying resin, at least a initiation and/or promote autoxidizable siccative, water and randomly at least a negatively charged ion and/or nonionogenic tenside and/or at least a flocculation agent, be characterised in that, the air-dry branch-shape polymer of described at least a amphipathic by the following material of reaction a), b) and c) obtain:
A) have at least 4 terminal hydroxy group and therefore hydroxy functionality f be at least 4 poly-hydroxy dendroid core polymkeric substance, described poly-hydroxy dendroid core polymkeric substance
I) by at least a two, three or the poly-hydroxy monocarboxylic acid add to a kind of two, three or the poly-hydroxy core molecules on obtain, both mol ratios are to obtain having described hydroxy functionality f and comprise that a core molecules and at least one are bonded to described two, three or the poly-hydroxy core molecules on the poly-hydroxy branch-shape polymer in branching generation, or
Ii) by two, three or at least a trimethylene oxide open loop of polyol add to a kind of two, three or the poly-hydroxy core molecules on obtain, both mol ratios are to obtain having described hydroxy functionality f and comprise that a core molecules and at least one are bonded to described two, three or the poly-hydroxy core molecules on the poly-hydroxy branch-shape polymer in branching generation
B) at least a be bonded in the described dendroid core polymkeric substance at least one and at the most f-1 described terminal hydroxy group undersaturated carboxylic acid and
C) at least a at least one and the adducts of f-1 described terminal hydroxy group at the most that is bonded in the described dendroid core polymkeric substance, this adducts by at least a monoallcylated polyethylene glycol add to obtain at least a dicarboxylic acid or corresponding acid anhydrides and/or at least a vulcabond and
Described at least a non-amphipathic air-drying resin is a short oil, and air-dry Synolac of middle oil or long oil and described air-dry branch-shape polymer and described air-dry Synolac are present in the described air-dry water-based resin composition with the weight ratio of 1:99 to 99:1.
2. according to the air-dry water-based resin composition of claim 1, be characterised in that described at least a monoallcylated polyethylene glycol is a monomethylated polyethylene glycol.
3. according to the air-dry water-based resin composition of claim 1 or 2, be characterised in that the molecular weight of described at least a monoallcylated polyethylene glycol is at least 500.
4. according to the air-dry water-based resin composition of claim 1 or 2, be characterised in that the molecular weight of described at least a monoallcylated polyethylene glycol is 500-2500.
5. according to the air-dry water-based resin composition of claim 1, be characterised in that described at least a dicarboxylic acid or acid anhydrides are the aliphatic series of at least a linearity or branching, alicyclic or aromatic dicarboxylic acid or acid anhydrides.
6. according to the air-dry water-based resin composition of claim 1 or 5, be characterised in that described at least a dicarboxylic acid or acid anhydrides are hexanodioic acids, nonane diacid, fumaric acid, maleic anhydride, phthalic acid or acid anhydrides, m-phthalic acid, the tetrahydro-phthalic anhydride, the hexahydro-phthalic anhydride, succsinic acid or acid anhydrides, and/or sebacic acid.
7. according to the air-dry water-based resin composition of claim 1, be characterised in that described at least a unsaturated carboxylic acid is aliphatic linearity or the branching lipid acid that has 8-24 carbon atom on its main carbochain.
8. according to the air-dry water-based resin composition of claim 1 or 7, be characterised in that described at least a unsaturated carboxylic acid is a tall oil fatty acid, soya fatty acid, safflower lipid acid, Sunflower Receptacle lipid acid, cottonseed lipid acid, castor-oil plant lipid acid, oleic acid, linolic acid and/or linolenic acid.
9. according to the air-dry water-based resin composition of claim 1, be characterised in that the weight ratio of described air-dry branch-shape polymer and described air-dry Synolac is 10:90 to 90:10.
10. according to the air-dry water-based resin composition of claim 1, be characterised in that the weight ratio of described air-dry branch-shape polymer and described air-dry Synolac is 20:80 to 80:20.
11. the air-dry water-based resin composition according to claim 1 is characterised in that the weight ratio of described air-dry branch-shape polymer and described air-dry Synolac is 30:70 to 70:30.
12. the air-dry water-based resin composition according to claim 1 is characterised in that the weight ratio of described air-dry branch-shape polymer and described air-dry Synolac is 50:50.
13. the air-dry water-based resin composition according to claim 1 is characterised in that, described at least a siccative is at least a metal drier.
14. the air-dry water-based resin composition according to claim 13 is characterised in that, described at least a metal drier is Pb, Zr, Co, Li, K, Mn or Mg siccative or their combination.
15. the air-dry water-based resin composition according to claim 13 or 14 is characterised in that, described at least a metal drier exists with the amount of 0.01-0.3wt%, in the metal on the solid resin.
16. the air-dry water-based resin composition according to claim 13 or 14 is characterised in that, described at least a metal drier exists with the amount of 0.05-0.1%, in the metal on the solid resin.
17. the air-dry water-based resin composition according to claim 1 is characterised in that, described optional at least a tensio-active agent exists with the amount of 1-15wt%, in the metal on the solid resin.
18. the air-dry water-based resin composition according to claim 1 is characterised in that, described optional at least a tensio-active agent exists with the amount of 2-10wt%, in the metal on the solid resin.
19. produce method, be characterised in that described method comprises according to the air-dry water-based resin composition of claim 1:
I) with described at least a air-dry branch-shape polymer, described at least a air-dry Synolac and randomly at least a flocculation agent be 40-80 ℃ of mixing, up to obtaining uniform mixture,
Ii) add and mix described at least a siccative and randomly described at least a tensio-active agent and/or at least a neutralizing agent,
Iii) with described component 40-80 ℃ mixed 10-60 minute and
Iv) under violent stirring, 40-80 ℃ water is added lentamente up to desired final solid content and/or viscosity.
20. the method according to claim 19 is characterised in that, described neutralizing agent is amine or ammonia.
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